Synthesis and study of azo dye compounds: variation of mesogenic behaviour with length of alkyl chains

The mesogenic behaviours of two azo dye liquid crystals, 1 and 4, differ because of the different length of terminal alkyl chains; azo dye 1 shows a SmB phase, azo dye 4 shows nematic and SmA phases during thermal processing. The molecular stackings of these two azo dye liquid crystals are compared on the basis of crystallographic studies to explain such unexpected mesogenic behaviour.     

Synthesis and Phase Behavior of Azo Dye Containing Liquid Crystalline Polyorganosiloxane

Abstract

A series of liquid crystalline polyorganosiloxanes containing both azo dye and cholesteryl groups were synthesized by reacting poly[3- chloroformylpropyl)methylsiloxane-co-dimethylsiloxane] with both cholesterol and 4-(4′-methoxyphenylazo)phenol. The yields were between 73 and 81%. Most of these new polyorganosiloxanes are colored solid products. Their chemical structures were confirmed by IR, ¹H NMR, and elemental analysis. Their phase behaviors were also investigated by using differential scanning calorimetry (DSC) and polarizing microscopy. The results show that all these polyorganosiloxanes exhibit liquid crystalline behavior at various temperatures and at any azo dye content. As a result of the orientation of both mesogenic azo dye and cholesteryl groups, smectic phases were formed beginning around 0°C, and cholesteric phases appeared above 60°C.     

N,N-Disubstituted-4-aminophenylazostyrylformate derivatives: their synthesis,mesogenic behaviour and photostability

A series of new azo dye liquid crystals was prepared by the reaction of the N,N-disubstituted-4-aminophenylazobenzaldehydes with butyl cyanoacetate in the presence of piperidine in refluxing ethanol. The new azo dye liquid crystals possess a SmA phase, and representative samples were found to be reasonably photostable.     

Non-conventional multi-arm ester liquid crystal derived from cholic acid: synthesis,thermal and optical behaviour

ABSTRACT

With cholic acid as the core, five multi-arm ester liquid crystals were synthesised with different terminal substituents. B₁–B₅ were mesogenic arms which were linked to multifunctional chiral core cholic acid. The effect of electron-withdrawing and electron-donating groups on the mesogenic behaviour of the compounds was discussed. All products were structurally well characterised by elemental analysis, ¹HNMR, and FT-IR. The phase behaviours were investigated by means of polarised optical microscopy and differential scanning calorimetry. B₂, B₄, B₅ and C₂, C₄, C₅ and D₂, D₄, D₅ exhibited typical nematic texture and belonged to thermotropic enantiotropic nematic liquid crystals. B₃, C₃ and D₃ also displayed typical nematic texture of thermotropic monotropic nematic liquid crystal. B₁, C₁ and D₁ did not have mesogenic performance. Wider mesogenic range for 81.6°C of C₅ whose terminal substituent is nitro on heating cycle while 121.1°C on cooling cycle. The results indicated that terminal substituents have a pretty important effect on the mesogenic phase and range of multi-arm liquid crystal compounds. The mesomorphic behaviour of compounds with polar groups terminally substituted performance much better than those without polar groups. In this ester multi-arm liquid crystal system, electron-withdrawing groups terminally substituted behave better than those electron-donating groups substituted.     

N,N-Disubstituted-4-aminophenylazostyrylformate derivatives: their synthesis, mesogenic behaviour and photostability

A series of new azo dye liquid crystals was prepared by the reaction of the N,N-disubstituted-4-aminophenylazobenzaldehydes with butyl cyanoacetate in the presence of piperidine in refluxing ethanol. The new azo dye liquid crystals possess a SmA phase, and representative samples were found to be reasonably photostable.     

New Synthesis of N,N‐Disubstituted (4‐Aminophenyl)diazenyl‐1,3,4‐thiadiazole,and Mesogenic Study and Molecular Modeling of Its H‐Bonded Complexes with a Series of m‐Alkoxybenzoic Acid Derivatives

A new N,N‐disubstituted (4‐aminophenyl)diazenyl‐1,3,4‐thiadiazole, an azo dye, was synthesized from the reaction of the 1‐decanoyl‐4‐phenylpiperazine in acetone, in situ, with the diazonium salt prepared from 1,3,4‐thiadiazol‐2‐amine and NaNO₂ in H₃PO₄. The azo dye was found to form complexes with a series of m‐alkoxybenzoic acid by intermolecular H‐bonding. The mesogenic behavior of the complexes were investigated by polarizing optical microscopy and differential scanning calorimetry. A study of the representing complex by powder X‐ray diffraction and molecular modeling was further undertaken to locate the H‐bonding position.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Abstract

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

Evaluation of Thermal and Analytical Properties of Two Liquid Crystals in Capillary GC

Comparative gas chromatographic applications of two new liquid crystals were investigated. The characterization of the two mesogenic compounds was performed with ¹H NMR and mass spectrometry. The thermal properties were established by differential scanning calorimetry. The optical characterization of the liquid crystal was made by using polarizing optical microscopy. The chromatographic separation abilities of the mesogenic compounds were studied using fused silica capillary columns. Interesting analytical performances were obtained notably in the separation of volatile aroma compounds and derivatives phenols.     

Synthesis and characterization of chiral azo LCPs with optical properties

ABSTRACT

In this study, we designed, synthesised and characterised two series of cholesteric liquid crystal polymers, QP series and ZP series. With polymethylhydrosiloxane as the main chain, QP series were synthesised by copolymerisation between the monomer M₁ containing a cholesteryl mesogenic unit and the monomer M₂ with a hydroxyl. ZP series, meanwhile, were synthesised by esterification between QP series members and the monomer M₃, a carboxylic acid with an azo mesogenic unit. We characterised chemical structures of all the monomers and polymers by FT-IR and ¹H-NMR, which proved that the target monomers and polymers had been obtained. We observed dramatic colour changes after the introduction of monomer M₃ and Grandjean textures from both QP series and ZP series using POM. In addition, strong selective reflection could be observed as well. Then, we characterised the thermal properties of polymers by DSC, TGA and XRD to explore their phase transition behaviours further. Their photoresponsive and photochromic properties were characterised by UV-Vis spectrum.     

Enantiopure Trioxadecalin Derived Liquid Crystals: Influence of the Nature of the Phenyl Substituent on the Mesogenic Properties

Reaction of pseudo‐glucal 1 with Grignard reagents derived from 1‐bromo‐4‐(trimethylsilyloxy)benzene, 1‐bromo‐4‐methoxybenzene, 1‐bromo‐4‐methoxymethoxybenzene, 1‐bromo‐4‐dimethylaminobenzene, in the presence of a catalytic amount of NiCl₂(dppe), gives the corresponding unsaturated β‐C‐aryl glycosides 2. Desilylation and hydrogenation of 2 leads to β‐C‐aryl glycosides 4, which can be used as chiral precursor compounds in the synthesis of chiral liquid crystals. Combination of 4 with arylaldehydes leads to compounds 5–7, whereas reaction with p‐alkoxysubstituted phenylboronic acids gives the trioxaboradecalins 8–11. The mesogenic properties of these compounds are strongly influenced by the nature of the substituent on the phenyl ring in the molecule.     

基于季戊四醇的三代硅碳烷液晶树状物研究

用发散法合成了季戊四醇-四烯丙基醚为核、周边含硝基偶氮苯介晶基元(M-NO₂)端基的新型三代硅碳烷液晶树状物PCSi-3G-NO₂, 并利用元素分析、红外光谱(IR)、核磁共振(NMR)、偏光显微镜(POM)、差示扫描量热法(DSC)和X射线衍射(XRD)进行表征. PCSi-3G-NO₂显示胆甾相和近晶S_E相, 其液晶相行为是K57S_E115I100Ch80S_E53K. 而对应的介晶基元M-NO₂显示向列相, 二者在熔点、清亮点和液晶态温区等方面差别较大.     

ENANTIOPURE TRIOXADECALIN DERIVED LIQUID CRYSTALS: INFLUENCE OF PHENYL SUBSTITUTION ON THE MESOGENIC PROPERTIES

Nickel(0)-catalyzed reaction of pseudo-glucal 1 with Grignard reagents derived from bromobenzene and 1-bromo-4-phenylbenzene gives the corresponding β-C-aryl glycosides 2. Desilylation and hydrogenation of 2 leads to saturated β-C-aryl glycosides 4, which can be used as chiral intermediates in the synthesis of chiral liquid crystals. The combination with p-alkoxy-substituted benzaldehyde leads to compounds 5–6. Alternatively, reaction with p-alkoxy-substituted phenylboronic acids gives the bora analogues 7–9. The mesogenic properties of these compounds are strongly influenced by the presence of an additional phenyl ring in the molecule.     

New hydrogen-bonded comblike polyimides with mesogenic side chains for stable orientation and fast switching of liquid crystals

ABSTRACT

New supramolecular comblike polyimides with mesogenic side chains for stable homeotropic orientation and fast electro-optical switching of liquid crystals (LCs) have been prepared through selective intermolecular hydrogen bonding between 4-(4-heptylphenyl)benzoic acid (4HPB) and host polyimide. A low concentration of 4HPB as the mesogenic guest molecule was hydrogen-bonded to polyimide backbone leading to the self-assembled comblike polyimide with enhanced homeotropic orientation properties. The electro-optical characteristics of the LC device containing hydrogen-bonded comblike polyimide exhibited better performance than those of LC cell with conventional polyimide. Because the conventional covalent approach for preparation of polyimides requires considerable synthetic efforts to achieve new functionality in polyimide materials, the proposed noncovalent method is a simple one and highly cost effective. Our controlled methodology should find wide application for the fabrication of functional alignment materials requiring high orientation ability.     

Unusual electro-optical behaviour of the nematic polyacrylate

ABSTRACT

High sensitivity of liquid crystals to the electric field makes them highly demanded and widely used in different applications. Despite the large number of the electro-optical research on the low-molar-mass liquid crystals electro-optics of the liquid crystalline (LC) polymers is much less studied. Herein, the comparative electro-optical behaviour of two nematic comb-shaped polyacrylates with phenylbenzoate mesogenic side groups was studied in detail. These two polyacrylates have completely the same structure of polymer backbone and spacer length but different in the direction of the ester group in the phenylbenzoate fragments. It was found that this difference predetermines their completely opposite electro-optical properties.

The influence of the electric field of different strength and frequency on the orientation of the mesogenic groups of these polymers is studied. It is shown that application of the electric field at temperatures above the glass transition temperature (~25°C) induces reorientation of the mesogenic groups along or perpendicular to the electric field direction depending in its turn on the ester group direction. For one of the polyacrylates an unusual textural transition is found; during cooling of the polymer sample under applied field at definite temperature a sharp change in the mesogen’s orientation from homeotropic to planar one is found. This electro-optical phenomenon is observed for the first time and probably associated with sharp change in sign of anisotropy of dielectric permittivity from positive (at high temperatures) to negative one (at lower temperatures). Kinetics of the electro-optical switching at different temperatures, influence of the molar masses of the polymer and frequency of the applied AC field on electro-optical behaviour of the polymers are studied. The possibility of the fixation of the electroinduced homeotropic alignment of the mesogenic groups by photopolymerisation of the diacrylate dissolved in the polymer is demonstrated.     

Fast-switching ferrolectric liquid crystalline polymers containing one or two centres of chirality in the side chain

In a liquid crystalline side chain polyacrylate containing one center of chirality in the terminal alkyl chain of the mesogenic part, switching times of 200–400 μs were measured in the SmC^* phase. Below this phase an unidentified phase exists, which shows electroclinic-like switching. The phase transition between those two phases can be shifted by applying an electric field. At higher molecular weights three subphases emerge in the SmC^* region. Variation of the spacer length revealed, for the first time, ferroelectric switching even at a spacer length of only two CH₂ groups. By shifting the centre of chirality into the spacer of the side group a polymer resulted, which shows electroclinic switching in the SmC^* phase, changing to ferroelectric switching when the voltage is increased. Incorporation of an oxirane ring as chiral building block into the spacer yielded a polymer that shows a sign inversion of the spontaneous polarization in the SmC^* phase. A polymer containing a dioxolane carbonic ester as chiral unit exhibits three switching states, with the third state existing at a low or zero electric field. This phenomenon is known for antiferroelectric liquid crystals. By doping a racemic LC polymer with a chiral monomeric LC we induced a spontaneous polarization. Colored FLC polymers were obtained by two different approaches. In an FLC–dye copolymer, increasing switching speed in three different chiral smectic phases was observed when increasing the dye concentration.     

Bent‐shaped liquid crystals containing a furan bridge in the mesogenic core

We report the synthesis and characterization of hitherto unreported bent‐shaped dimeric liquid crystals based on a furan bridge in the mesogenic core. The compound 18‐Fu2 exhibits liquid crystalline behaviour.     

偶氮苯为探针的液晶聚合物聚集形态研究

利用紫外-可见光谱,对比研究了尾挂侧链液晶聚合物和腰挂侧链液晶聚合物在结晶相和液晶相转变过程中的液晶基元取向情况.研究表明,石英基材表面倾向于诱导偶氮液晶基元垂直于基材排列;观察到了在液晶态尾挂侧链液晶聚合物和腰挂侧链液晶聚合物的不同取向行为.在室温下重新结晶数天后,腰挂液晶聚合物的紫外可见光谱缓慢回复.     

Azo compounds and Schiff 's bases derived from 5-(4-pyridyl)-2-amino-1,3,4-thiadiazole: synthesis,mesomorphic properties and structural study by semi-empirical calculations

The synthesis and liquid crystalline properties of new Schiff 's bases (series 3a-f) and azo compounds (4a-f) incorporating pyridine and 1,3,4-thiadiazole rings are reported. The first homologues in the series of Schiff's bases (3a-c) show a monotropic mesophase and the homologues 3d-f display an enantiotropic SmA phase. The only azo compounds to exhibit liquid crystalline properties are the homologues 4e, f which show a monotropic nematic phase. These series are compared with Schiff's bases and azo compounds analogues (series 5 and 6), previously reported by us and an AM1 study of the structure/mesomorphic property relationship is described.     

Synthesis and Study of Azo‐Dye Compounds: Various Molecular Stackings from Different Polarities of the Molecules

One non‐F‐containing and two F‐containing azo‐dye compounds were prepared to investigate their molecular stackings by X‐ray crystallography. Introduction of the F‐atom into the aromatic moiety of azo‐dye compounds leads to a variation of the charge distribution and consequently to different molecular stackings. Accordingly, the mesogenic behaviors in the solid state are different.